CH19 Thermodynamics

Chapter 19: Thermodynamics
Chemistry: The Molecular Nature of

Matter, 6E
Jespersen/Brady/Hyslop
Thermodynamics
Study of energy changes and flow of energy
Answers several fundamental questions:
Is it possible for reaction to occur?
Will reaction occur spontaneously (without outside
interference) at given T?
Will reaction release or absorb heat?
Tells us nothing about time frame of reaction
Kinetics
Two major considerationsmust be balanced
Enthalpy changes, H (heats of reaction)
Heat exchange between system and surroundings
Nature's trend to randomness or disorder
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Review of First Law of Thermodynamics
Internal energy, E
System's total energy
Sum of KE and PE of all particles in system
E system (KE )system (PE )system

E Efinal Einitial
or for chemical reaction
E Eproducts Ereactants
E + energy into system
E energy out of system

Two Methods of Energy Exchange
Between System and Surroundings
Heat q Work w
E = q + w
Conventions of heat and work
q + Heat absorbed by system Esystem

q Heat released by system Esystem
w + Work done on system Esystem
w Work done by system Esystem

First Law of Thermodynamics
Energy can neither be created nor destroyed
It can only be converted from one form to another
KE PE
Chemical Electrical
Electrical Mechanical
E and E are state functions
Path independent
E = q + w
E system (KE )system (PE )system

Work in Chemical Systems
1. Electrical
2. Pressure-volume or PV
w = PV
Where P = external pressure
If PV only work in chemical system, then
E q ( P V ) q P V

Heat at Constant Volume
Reaction done at constant V
V = 0
PV = 0, so
E = qV
Entire E change due to heat absorbed or lost
Rarely done, not too useful

Heat at Constant Pressure
More common
Reactions open to atmosphere
Constant P
Enthalpy
H = E + PV
Enthalpy change
H = E + PV
Substituting in first law for E gives
H = (q PV) + PV = qP
H = qP
Heat of reaction at constant pressure

Converting Between E and H For
Chemical Reactions
H E
Differ by H E = PV
Only differ significantly when gases formed or
consumed
Assume gases are ideal
nRT nRT
V V
P P
Since P and T are constant
RT
V n
P
Converting Between E and H For
Chemical Reactions
When reaction occurs
V caused by n of gas
Not all reactants and products are gases
So redefine as ngas
Where ngas = (ngas)products (ngas)reactants
Substituting into H = E + PV gives
or RT
H E P ngas
P
H E ngas RT
Ex. 1. What is the difference between H and
E for the following reaction at 25 C?
2 N2O5 (g) 4 NO2 (g) + O2 (g)
What is the % difference between H and E?
Step 1: Calculate H using Hf data (Table 7.2)
Recall
H 4H f (NO2 ) H f (O2 ) 2H f (N 2O5 )
H (H f ) products (H f )reactants
H = (4 mol)(33.8 kJ/mol) + (1 mol)(0.0 kJ/mol) (2
mol)(11 kJ/mol)
H = 113 kJ

Ex. 1. (cont.)
Step 2: Calculate
ngas = (ngas)products (ngas)reactants
ngas = (4 + 1 2) mol = 3 mol
Step 3: Calculate E using
R = 8.31451 J/Kmol T = 298 K
E H ngas RT
E = 113 kJ
(3 mol)(8.31451 J/Kmol)(298 K)(1 kJ/1000 J)
E = 113 kJ 7.43 kJ = 106 kJ

Ex. 1. finish
Step 4: Calculate % difference
7.43kJ
% difference 100% 6.6%
113kJ
Bigger than most, but still small
Note: Assumes that volumes of solids and liquids are

negligible
Vsolid Vliquid << Vgas

Is Assumption that Vsolid Vliquid << Vgas
Justified?
Consider
CaCO3(s) + 2H+(aq) Ca2+(aq) + H2O(l) + CO2(g)
37.0 mL 2*18.0 mL 18 mL 18 mL 24.4 L
Volumes assuming each coefficient equal

number of moles
So V = Vprod Vreac = 24.363 L 24.4 L
Yes, assumption is justified
Note: If No gases are present reduces to
E H
Learning Check
Consider the following reaction for picric acid:
8O2(g) + 2C6H2(NO2)3OH() 3 N2(g) + 12CO2(g) + 6H2O()
What type of reaction is it?
Calculate ,
8O2(g) + 2C6H2(NO2)3OH() 3N2(g) + 12CO2(g) + 6H2O()
f
(kJ/mol) 0.00 3862.94 0.00 -393.5 -241.83
H0 = 12mol(393.5 kJ/mol) + 6mol(241.83kJ/mol) +
6mol(0.00kJ/mol) 8mol(0.00kJ/mol) 2mol(3862.94kJ/mol)
H0 = 13,898.9 kJ
= H ngasRT = H (15 8)mol*298K*8.314103kJ/(molK)
= 13,898.9 kJ 29.0 kJ = 13,927.9 kJ

Your Turn!
Given the following:
3H2(g) + N2(g) 2NH3(g) Ho = -46.19 kJ mol-1
Determine E for the reaction.
A. -51.14 kJ mol-1
B. -41.23 kJ mol-1
C. -46.19 kJ mol-1
D. -46.60 kJ mol-1
H = E + nRT E = H - nRT
E =-46.19 kJ mol
(-2 mol)(8.314 J K-1mol-1)(298K)(1 kJ/1000 J)
E = -51.14 kJ mol-1
Enthalpy Changes and Spontaneity
What are relationships among factors that influence
spontaneity?
Spontaneous Change
Occurs by itself
Without outside assistance until
finished
Ex.
Water flowing over waterfall
Melting of ice cubes in glass
on warm day

Nonspontaneous Change
Occurs only with outside assistance
Never occurs by itself:
Room gets straightened up
Pile of bricks turns into a brick wall
Decomposition of H2O by electrolysis
Continues only as long as outside assistance occurs:
Person does work to clean up room
Bricklayer layers mortar and bricks
Electric current passed through H2O

Nonspontaneous Change
Occur only when
accompanied by some
spontaneous change
You consume food,
spontaneous biochemical
reactions occur to supply
muscle power
to tidy up room or
to build wall
Spontaneous mechanical or
chemical change to generate
electricity

Reaction Rate and Spontaneity
H indicates if reaction has tendency to occur
Rate of reaction also plays role
Some very rapid:
Neurons firing in nerves in response to pain
Detonation of stick of dynamite
Some gradual:
Erosion of stone
Ice melting
Iron rusting
Some so slow, appear to be nonspontaneous:
Gasoline and O2 at RT
Many biochemical processes
Direction of Spontaneous Change
Many reactions which occur spontaneously are
exothermic:
Iron rusting
Fuel burning
H and E are negative
Heat given off
Energy leaving system
Thus, H is one factor that influences spontaneity

Direction of Spontaneous Change
Some endothermic reactions occur spontaneously:
Ice melting
Evaporation of water from lake
Expansion of CO2 gas into vacuum
H and E are positive
Heat absorbed
Energy entering system
Clearly other factors influence spontaneity

Thermodynamic vs. Kinetics
Thermodynamics tells us:
Direction of reaction Domain of Thermodynamics
(initial and final states)
Is it possible for reaction to Domain of Kinetics
occur? (reaction pathway)
Will reaction occur
spontaneously at
given T?
Energy
Will reaction release
or absorb heat? Reactants
Kinetics tells us:

Products
Speed of reaction
Reaction Progress
Pathway between reactants
and products
Your Turn!
We can expect the combustion of propane
to be:
A. spontaneous
B. non-spontaneous
C. neither

Heat Transfer Between Hot and Cold
Objects (Ch 7)
Consider system of two objects
Initially one hot and one cold
Hot = higher KEave of molecules = faster
Cold = lower KEave of molecules = slower
When they collide, what is most likely to occur?
Faster objects bump into colder objects and transfer energy
so
Hot objects cool down and slow down
Cold objects warm up and speed up
The reverse doesnt occur

Heat Transfer Between Hot and Cold
Objects
Result:
Heat flows spontaneously from hot to colder object
Heat flows because of probable outcome of intermolecular
collisions
Spontaneous processes tend to proceed from states of low
probability to states of higher probability
Spontaneous processes tend to disperse energy

Entropy (symbol S)
Thermodynamic quantity
Describes number of equivalent ways that energy can be
distributed
Quantity that describes randomness of system
Greater statistical probability of particular state means
greater the entropy!
Larger S, means more random and more probable

Fig. 19.6 - 20 E units per system
Low Entropy High Entropy
A absorbs E in units of 10 More ways to distribute E
Few ways to distribute E B absorbs E in units of 5
represent Es of represent Es of
molecules of A molecules of B

Entropy
If Energy = money
Entropy (S) describes number of different ways of
counting it
Criterion for Spontaneity
Clear order to things
Things get rusty spontaneously
Don't get shiny again
Sugar dissolves in coffee
Stir moreit doesn't undissolve
Ice liquid water at RT
Opposite does NOT occur
Fire burns wood, smoke goes up chimney
Can't regenerate wood
Common factor in all of these:
Increase in randomness and disorder of system
Something that brings about randomness more
likely to occur than something that brings order

Entropy, S
Measure of randomness and disorder
Measure of chaos
State function
Independent of path
S = Change in Entropy
Also state function
S Sfinal Sinitial
For chemical reaction
S Sproducts Sreactants

Entropy
Sproducts > Sreactants means S +
Entropy 's
Probability of state 's
Randomness 's
Favors spontaneity
Sproducts < Sreactants means S
Entropy 's
Probability of state 's
Randomness 's
Does not favor spontaneity
Any reaction that occurs with in entropy tends to
occur spontaneously

Effect of Volume on Entropy
For gases, Entropy as Volume

A. Gas separated from vacuum by partition
B. Partition removed
C. Gas expands to achieve more probable particle
distribution
More random, higher probability, more positive S
Effect of Temperature on Entropy
As T , entropy
A. T = 0 K, particles () in equilibrium lattice positions and S
relatively low
B. T > 0 K, molecules vibrate, S
C. T further, more violent vibrations occur and S higher than in
B

Effect of Physical State on Entropy
Crystalline solid very low S
Liquid higher S, molecules can move freely
More ways to distribute KE among them
Gas highest S, particles randomly distributed throughout
container
Many, many ways to distribute KE

Your Turn!
Which represents an increase in entropy?
A. water vapor condensing to liquid

B. carbon dioxide subliming
C. liquefying helium gas
D. proteins forming from amino acids

Entropy Affected by Number of Particles
Adding particles to system
number of ways energy can be distributed in system
So all other things being equal
Reaction that produces more particles will have positive
S

Summary
Larger V, greater S
Expansion of gas S +
Higher T, greater S
Higher T, means more KE in particles, move more, so random
distributions favored
Ssolid < Sliquid << Sgas
Solids more ordered than liquids, which are much more ordered
than gases
Reactions involving gases
Simply calculate change in number of mole gas,
ngas
If ngas + , S +
If ngas , S
Entropy Changes in Chemical Reactions
Ex. N2 (g) + 3 H2(g) 2 NH3(g)
nreactant = 4 nproduct = 2
n = 2 4 = 2
Predict Srxn < 0
Higher positional Lower positional

probability probability
Entropy Changes in Chemical Reactions
Reactions without gases
Simply calculate number of mole molecules
n = nproducts nreactants
If n + , S +
If n , S
More molecules, means more disorder
Usually the side with more molecules, has less complex
molecules
Smaller, fewer atoms per molecule

Ex. 2 Predict Sign of S for Following
Reactions
CaCO3(s) + 2H+ (aq) Ca2+(aq) + H2O(l) + CO2(g)
ngas = 1 mol 0 mol = 1 mol
ngas +, S +
2 N2O5 (g) 4 NO2 (g) + O2 (g)
ngas = 4 mol + 1 mol 2 mol = 3 mol
ngas +, S +
OH (aq) + H+ (aq) H2O (l)
ngas = 0 mol
n = 1 mol 2 mol = 1 mol
n , S

Predict Sign of S in Following:
Dry ice carbon dioxide gas
CO2(s) CO2(g) positive
Moisture condenses on a cool window
H2O(g) H2O() negative

AB A + B
positive
A drop of food coloring added to a glass of water
disperses
positive
2Al(s) + 3Br2() 2AlBr3(s)
negative

Your Turn!
Which of the following has the most entropy at standard
conditions?
A. H2O()
B. NaCl(aq)
C. AlCl3(s)
D. Cant tell from the information

Your Turn!
Which reaction would have a negative entropy?
A. Ag+(aq) + Cl-(aq) AgCl(s)

B. N2O4(g) 2NO2 (g)
C. C8H18(l ) + 25/2 O2(g) 8CO2(g) + 9H2O(g)
D. CaCO3(s) CaO(s) + CO2(g)

Both Entropy and Enthalpy Can Affect
Reaction Spontaneity
Sometimes they work together
Building collapses
PE H
Stones disordered S +
Sometimes work against each other
Ice melting (ice/water mix)
Endothermic
H + nonspontaneous
Disorder of molecules
S + spontaneous

Which Prevails?
Hard to telldepends on temperature!
At 25 C, ice melts
At 25 C, water freezes
So three factors affect spontaneity:
H
S
T

Second Law of Thermodynamics
When a spontaneous event occurs, total entropy of
universe s
(Stotal > 0)
In a spontaneous process, Ssystem can decrease as long
as total entropy of universe increases
Stotal = Ssystem + Ssurroundings
It can be shown that
q surroundings
S surroundings
T
Does This Make Sense?
Yes?
As heat added
Disorder or entropy , S q
But how much T, S, depends on T at which it occurs
Low T, larger S
High T, smaller S
S 1/T

Your Turn!
When ice melts in your hand (assume your hand is 30o C),
A. the entropy change of the system is less then the
entropy change of the surroundings.
B. the entropy change of the surroundings is less than the
entropy change of the system.
C. the entropy change of the system equals the entropy
change of the surroundings.
Ssys = H/273K Ssurr = H/303K
Ssys > Ssurr

Law of Conservation of Energy
Says q lost by system must be gained by surroundings
qsurroundings = qsystem
If system at constant P, then
qsystem = H
So
qsurroundings = Hsystem
and
q surroundings H system
S surroundings
T T
Thus Entropy for Entire Universe is
H system
S total S system
T
Multiplying both sides by T we get
TStotal = TSsystem Hsystem
or
TStotal = (Hsystem TSsystem)
For reaction to be spontaneous
TStotal > 0 (+)
So,
(Hsystem TSsystem) < 0
() for reaction to be spontaneous

Gibbs Free Energy
Would like one quantity that includes all three factors that
affect spontaneity of a reaction
Define new state function
Gibbs Free Energy
Maximum energy in reaction that is "free" or available to do
useful work
G H TS
At constant P and T, changes in free energy G = H TS

Gibbs Free Energy
G = H T S
G <0 Spontaneous process
G =0 At equilibrium
G >0 Nonspontaneous
G state function
Made up of T, H and S = state functions
Has units of energy
Extensive property
G = Gfinal Ginitial
Criteria for Spontaneity?
At constant P and T, process spontaneous only if it is
accompanied by in free energy of system
H S Spontaneous?
+ G = () [T(+)] = Always, regardless of T
+ G = (+) [T()] = + Never, regardless of T
+ + G = (+) [T(+)] = ? Depends; spontaneous at
high T, G
G = () [T()] = ? Depends; spontaneous at
low T, G

Summary
When H and S have
same sign, T determines
whether spontaneous or
non-spontaneous
Temperature-controlled
reactions are spontaneous
at one temperature and
not at another

Your Turn!
At what temperature (K) will a reaction become non-
spontaneous when H = -50.2 kJ mol-1 and
S = +20.5 J K-1 mol-1 ?
A. 298 K
B. The reaction cannot become non-spontaneous at any
temperature
C. 1200 K
D. 2448 K

Third Law of Thermodynamics
At absolute zero (0 K),
Entropy of perfectly ordered, pure crystalline substance is
zero
S = 0 at T = 0 K
Since S = 0 at T = 0 K
Define absolute entropy of substance at higher temperatures
Standard entropy, S
Entropy of 1 mole of substance at 298 K (25C) and 1 atm
pressure
S = S for warming substance from 0 K to 298 K (25C)

Consequences of Third Law
1. All substances have positive entropies as they are more
disordered than at 0 K
Heating randomness
S is biggest for gasesmost disordered
2. For elements in their standard states
S 0 (but Hf = 0)
Units of S J/(molK)
Standard Entropy Change
To calculate S for reaction, do Hess's Law type
calculation
Use S rather than entropies of formation
S
n S (products ) m S (reactants)


Learning Check
Calculate S0 for the following:
CO2(s) CO2(g)
187.6 213.7 S0 (J/molK)
S0 = (213.7 187.6) J/molK
S0 = 26.1 J/molK
CaCO3(s) CO2(g) + CaO(s)
92.9 213.7 40 S0 (J/molK)
S0 = (213.7 +40 92.9) J/molK
S0 = 161 J/molK
Ex. 3. Calculate S for reduction of aluminum oxide
by hydrogen gas
Al2O3 (s) + 3 H2 (g) 2 Al (s) + 3 H2O (g)
Substance S (J/ Kmol)
Al (s) 28.3
Al2O3 (s) 51.00
H2 (g) 130.6
H2O (g) 188.7
S p products r reactants
n S
n S
S [2S Al

(s ) 3S
H 2O ( g ) ]
[S Al

2O 3 ( s )
3S
H 2 (g ) ]
Ex. 3
28.3 J 188.7 J
S
2 mol * 3 mol *
mol K mol K
51.00 J 130.6J
1 mol * 3 mol *
mol K mol K
S = 56.5 J/K + 566.1 J/K 51.00 J/K

391.8
S = 179.9 J/K

Your Turn!
What is the entropy change for the following
reaction?
Ag+(aq) + Cl-(aq) AgCl(s)
72.68 56.5 96.2 So(J K-1 mol-1)
A. +32.88 J K-1 mol-1
B. -32.88 J K-1 mol-1
C. -32.88 J mol-1
D. +112.38 J K-1 mol-1
So = [96.2 (72.68 + 56.5)] J K-1 mol-1
So = -32.88 J K-1 mol-1

Standard Free Energy Changes
Standard Free Energy Change, G
G measured at 25 C (298 K) and 1 atm
Two ways to calculate, depending on what data is
available
Method 1. G = H (298.15 K)S
Ex. 4. Calculate G for reduction of aluminum oxide by
hydrogen gas
Al2O3(s) + 3 H2(g) 2 Al(s) + 3H2O(g)

Ex. 4. Method 1
Al2O3 (s) + 3 H2 (g) 2 Al (s) + 3 H2O (g)
Step 1: Calculate H for reaction using
Hf
Substance Hf (kJ/mol)
Al (s) 0.0
Al2O3 (s) 1669.8
H2 (g) 0.0
H2O (g) 241.8
H np Hf products nr Hfreactants
H [2H f Al(s ) 3H fH O(g ) ]
2
[H f Al O (s )

3H f H ( g ) ]

2 3 2
Ex. 4. Method 1 Step 1 (H)
0.00 kJ 241.8 kJ
H 2 mol* 3 mol*
mol mol
1669.8 kJ 0.00 kJ
1 mol* 3 mol*
mol mol
H = 0.0 kJ 725.4 kJ 0.00 kJ

( 1669.8 kJ)
H = 944.4 kJ

Ex. 4 Method 1
Step 2: Calculate S see Ex. 4

S = 179.9 J/K
Step 3: Calculate
G = H (298.15 K)S
G = 944.4 kJ (298 K)(179.9 J/K)(1 kJ/1000 J)
G = 944.4 kJ 53.6 kJ = 890.8 kJ
G = +
not spontaneous

Method 2
Use Standard Free Energies of Formation

Gf
Energy to form 1 mole of substance from its elements in
their standard states at 1 atm and 25 C
G

np Gf products
nr Gf reactants

Ex. 4. Method 2
Calculate G for reduction of aluminum oxide by
hydrogen gas.
Al2O3 (s) + 3 H2 (g) 2 Al (s) + 3 H2O (g)
Substance Gf (kJ/mol)
Al (s) 0.0
Al2O3 (s) 1576.4
H2 (g) 0.0
H2O (g) 228.6
G [2G f Al(s ) 3G fH O(g ) ]

2
[G f Al O (s )

3G f H ( g ) ]

2 3 2
Ex. 4. Method 2
0. 00 kJ 228.6 kJ
G 2 mol* 3 mol*
mol mol
1576. 4 kJ 0. 00 kJ
1 mol* 3 mol*
mol mol
G = 0.0 kJ 685.8 kJ 0.00 kJ

( 1576.4 kJ)
G = 890.6 kJ
Both methods same within experimental error

Spontaneous Reactions Produce Useful
Work
Fuels burned in engines to power cars or heavy machinery
Chemical reactions in batteries
Start cars
Run cellular phones, laptop computers, mp3 players
Energy not harnessed if reaction run in an open dish
All energy lost as heat to surroundings
Engineers seek to capture energy to do work
Maximize efficiency with which chemical energy is converted to
work
Minimize amount of energy transformed to unproductive heat

Thermodynamically Reversible
Process that can be reversed and is always very close to
equilibrium
Change in quantities is infinitesimally small
Example - expansion of gas
Done reversibly, it does most work on surroundings

G = Maximum Possible Work
G is maximum amount of energy produced during a
reaction that can theoretically be harnessed as work
Amount of work if reaction done under reversible conditions
Energy that need not be lost to surroundings as heat
Energy that is free or available to do work

Ex. 5
Calculate G for reaction below at 1 atm and 25C,
given H = 246.1kJ/mol, S = 377.1 J/(molK).
H2C2O4(s) + O2(g) 2CO2(g) + H2O()
G25 = H TS
kJ J 1J
G 246.1

(298 K ) 377.1
mol K mol 1000kJ
G =(246.1 112.4)kJ/mol
G = 358.5kJ/mol

Your Turn!
Calculate Go for the following reaction,
H2O2(l ) H2O(l ) + O2(g)
given Ho = -196.8 kJ mol-1 and So = +125.72 J K-1
mol-1.
A. -234.3 kJ mol-1
B. +234.3 kJ mol-1
C. 199.9 kJ mol-1
D. 3.7 x 105 kJ mol-1
Go = -196.8 kJ mol-1 298 K (0.12572 kJ K-1 mol-1)
Go = -234.3 kJ mol
System at Equilibrium
Neither spontaneous nor nonspontaneous
In state of dynamic equilibrium
Gproducts= Greactants
G = 0
Consider freezing of water at 0o C
H2O() H2O(s)
System remains at equilibrium as long as no heat added or
removed
Both phases can exist together indefinitely
Below 0oC, G < 0 freezing spontaneous
Above 0oC, G > 0 freezing nonspontaneous
No Work Done at Equilibrium
G = 0
No free energy available to do work
Consider fully charged battery
Initially
All reactants, no products
G large and negative
Lots of energy available to do work
As battery discharges
Reactants converted to products
G less negative
Less energy available to do work
At Equilibrium
G = Gproducts Greactants = 0
No further work can be done
Dead battery
Phase Change = Equilibrium
H2O() H2O(g)
G = 0 = H TS
Only one temperature possible for phase change at
equilibrium
Solid-liquid equilibrium
Melting/freezing temperature (point)
Liquid-vapor equilibrium
Boiling temperature (point)
Thus H = TS and
or H
S
H T
T
S
Ex. 6
Calculate Tbp for reaction below at 1 atm and 25C, given H
= 31.0kJ/mol, S = 92.9 J/(molK)
Br2(l) Br2(g)
H 31.0kJ / mol
Tbp 334K
S
0.0929kJ /( mol K )
For T > 334 K, G < 0 and reaction is spontaneous (S
dominates)
For T < 334 K, G > 0 and reaction is nonspontaneous (H
dominates)
For T = 334 K, G = 0 and T = normal boiling point

Learning Check
What is the expected melting point for Cu?
Hf0 (kJ/mol) Gf0 (kJ/mol) S (J/molK)
Cu() 341.1 301.4 166.29
Cu(s) 0 0 33.1
Cu(s) Cu()
H = 1mol(341.1 kJ/mol 1mol(0 kJ/mol)
H = +341.1kJ
S = 1mol(166.29 J/molK 1mol(33.1 J/molK)
S = 133.19 J/K
341.1kJ
T 256.1K
0.13319kJ /K
Free Energy Diagrams
G > 0 Nonspontaneous
N2O4(g) 2NO2(g) Minimum indicates
composition of
equilibrium reaction
mixture
Because G +
Equilibrium lies closer
to reactants
Equilibrium occurs here

at Ptotal = 1 atm with
16.6% N2O4 decomposed
Free Energy Diagrams
G < 0 Spontaneous
Reaction proceeds
down hill from left
to right
Because G
Equilibrium lies closer
to products

G and Position of Equilibrium
When G > 0 (positive)
Position of equilibrium lies close to reactants
Little reaction occurs by the time equilibrium is reached
Reaction appears nonspontaneous
When G < 0 (negative)
Position of equilibrium lies close to products
Mainly products exist by the time equilibrium is reached
Reaction appears spontaneous

G and Position of Equilibrium
When G = 0
Position of equilibrium lies ~ halfway between products
and reactants
Significant amount of both reactants and products
present at time equilibrium is reached
Reaction appears spontaneous, whether start with
reactants or products
Can Use G to Determine Reaction Outcome
G large and positive
No observable reaction occurs
G large and negative
Reaction goes to completion

Learning Check
Ex. 7 Given that H = 97.6 kJ/mol,
S = 122 J/(molK), at 1atm and 298K, will the
following reaction occur spontaneously?
MgO(s) + 2HCl(g) H2O() + MgCl2(s)
G = H TS
= 97.6kJ/mol 298K(0.122 kJ/molK)
G = 97.6kJ/mol +36.4kJ/mol
= 61.2 kJ/mol

Effect of Temperature on G
Reactions often run at Ts other that 298 K
Position of equilibrium can change as G depends on T
G = H TS
For Ts near 298 K, expect only very small changes in H
and S
For reaction at T, we can write:
GT HT TST

GT H 298

TS 298


Ex. 8 Determining Effect of T on Spontaneity
Calculate G at 25C and 500C for the Haber process

N2 ( g) + 3 H2 (g) 2 NH3 (g)
Assume that H and S do not change with T
Solving Strategy
Step 1. Using data in Tables 6.2 and 18.2 calculate H and
S for the reaction at 25C
H = 92.38 kJ
S = 198.4 J/K

Step 2. Calculate G for the reaction at 25C using H and

S
N2 (g) + 3 H2 (g) 2 NH3 (g)
H = 92.38 kJ
S = 198.4 J/K
G = H TS
G = 92.38 kJ (298 K)(198.4 J/K)
1kJ
G = 92.38 kJ+ 59.1 kJ = 33.3 kJ
1000 J
So the reaction is spontaneous at 25C

Step 3. Calculate G for the reaction at 500C using H and

S.
T = 500C + 273 = 773 K
H = 92.38 kJ
S = 198.4 J/K
G = H TS
G = 92.38 kJ (773 K)(198.4 J/K) 1kJ
G = 92.38 kJ+ 153 kJ = 61 kJ
1000 J
So the reaction is NOT spontaneous at 500C

Ex. 8 Does this answer make sense?
G = H TS
H = 92.38 kJ
S = 198.4 J/K
Since both H and S are negative
At low T
G will be negative and spontaneous
At high T
TS will become a bigger positive number and
G will become more positive and thus eventually, at high
enough T, will become nonspontaneous

Effect of Change in Pressure or
Concentration on G
G at nonstandard conditions is related to G
at standard conditions by an expression that
includes reaction quotient Q
G G RT ln Q
This important expression allows for any

concentration or pressure
Recall:
y
[products ]
Q
[reactants ]x
Ex. 9 Calculating G at Nonstandard
conditions
Calculate G at 298 K for the Haber process
N2 (g) + 3 H2 (g) 2 NH3 (g) G = 33.3 kJ
For a reaction mixture that consists of 1.0 atm N2, 3.0
atm H2 and 0.5 atm NH3
Step 1 Calculate Q
2 2
P (0.50) 3
Q 9.3 10
NH 3
3 3
P P
N2 H 2 (1.0)(3.0)

Ex. 9 Calculating G at Nonstandard
conditions
Step 2 Calculate G = G + RT lnQ
G = 33.3 kJ/mol + (8.314J/Kmol)*(1kJ/1000J)*
(298K)*ln(9.3 103)
= 33.3 kJ/mol + (2.479 kJ/mol)*ln(9.3 103)
= 33.3 kJ + (11.6 kJ/mol)
= 44.9 kJ/mol
At standard conditions all gases (N2, H2 and NH3) are at 1
atm of pressure
G becomes more negative when we go to 1.0 atm N2, 3.0
atm H2 and 0.5 atm NH3
Indicates larger driving force to form NH3
Preactants > Pproducts
How K is related to G
Use relation G = G + RT lnQ to derive relationship
between K and G
At Equilibrium
G = 0 and Q = K
So 0 = G + RT lnK
G = RT lnK
Taking antilog (ex) of both sides gives
K = eG/RT

At Equilibrium
G = RT lnK and K = eG/RT
Provides connection between G and K
Can estimate Ks at various Ts if know G
Can get G in know Ks
Relationship between K and G
Keq G Reaction
>1 Spontaneous Favored
Energy released
<1 + non-spontaneous Unfavorable
Energy needed
=1 0 At Equilibrium
Ex. 10 Calculating G from K
Ksp for AgCl(s) at 25C is 1.8 1010 Determine G for
the process
Ag+ (aq) + Cl (aq) AgCl (s)
Reverse of Ksp equation, so
1 1 9
K 5.6 10
K sp 1.8 10 10
G = RT lnK = (8.3145J/Kmol)(298K)*
ln(5.6 109)*(1kJ/1000J)
G = 56 kJ/mol
Negative G indicates precipitation will occur

Ex. 11 Calculating K from G
Calculate K at 25C for the Haber process
N2 (g) + 3 H2 (g) 2 NH3 (g)
G = 33.3 kJ/mol = 33,300 J/mol
G / RT
K e
Step 1 Solve for exponent
G (33,300J / mol )
13.4
RT (8.3145J / K mol )(298K )
Step 2 Take ex to obtain K
G / RT 13.4 5
K e e 7 10
Large K indicates NH3 favored at RT

Your Turn!
Calculate the equilibrium constant for the
decomposition of hydrogen peroxide at 298 K given
Go = -234.3 kJ mol.
A. 8.5 x 10-42
B. 1.0 x 10499
C. 3.4 x 10489
D. 1.17 x 1041
G (234, 300 J / mol )
94.56
RT (8.3145J / K mol )(298K )
K e 94.56 1.17 x 10 41
Ex. 12 Calculating K from G, First
Calculate G
Calculate the equilibrium constant at 25C for the
decarboxylation of liquid pyruvic acid to form gaseous
acetaldehyde and CO2
O O
C OH C + CO2
H3C C H3C H

First Calculate G from Gf
Compound Gf, kJ/mol
CH3COH 133.30
CH3COCOOH 463.38
CO2 394.36
G Gf (CH 3COH ) Gf (CO2 ) Gf (CH 3COCOOH )

G 133.30 (394.36) (463.38)
G 64.28kJ


Next Calculate Equilibrium Constant

G RT
K e

G 64.28kJ 1000J
25.94
RT (8.314J / K )(298K ) kJ
( 25.945 ) 25.945
K e e
K = 1.85 1011
Temperature Dependence of K
G = RT lnK = H TS
Rearranging gives
H 1 S
ln K
R T R
Equation for line
Slope = H/RT
Intercept = S/R
Also way to determine
K if you know H and S

Ex. 12 Calculate K given H and S
Calculate K at 500 C for Haber process
N2 (g) + 3 H2 (g) 2 NH3 (g)
Given H = 92.38 kJ and S = 198.4 J/K
Assume that H and S do not change with T
H S
ln K
RT R
92,380 J 198.4 J / K
ln K
(8.314 J / K )(773K ) (8.314 J / K )
lnK = + 14.37 23.86 = 9.49
K = e9.49 = 7.56 105

Bond Energy
Amount of energy needed to break chemical bond into
electrically neutral fragments
Useful to know
Within reaction
Bonds of reactants broken
New bonds formed as products appear
Bond breaking
1st step in most reactions
One of the factors that determines reaction rate
Ex. N2 very unreactive due to strong N N bond

Bond Energies
Can be determined spectroscopically for simple
diatomic molecules
H2, O2, Cl2
More complex molecules, calculate using
thermochemical data and Hesss Law
Use Hformation enthalpy of formation
Need to define new term
Enthalpy of atomization or atomization energy,
Hatom
Energy required to rupture chemical bonds of 1 mole of
gaseous molecules to give gaseous atoms

Determining Bond Energies
Ex. CH4(g) C(g) + 4 H(g)
Hatom = energy needed to break all bonds in molecule
Hatom /4 = average bond CH dissociation energy in
methane
D = bond dissociation energy
Average bond energy to required to break all bonds in
molecule
How do we calculate this?
Use Hf for forming gaseous atoms from elements in
their standard states
Hesss Law

Determining Bond Energies
Path 1: bottom
Formation of CH4 from its elements = Hf
Path 2: top 3 step path
Step 1 break HH bonds
Step 2 break CC bonds
Step 3: form 4 CH bonds
1. 2H2(g) 4H(g) H1 = 4Hf (H,g)
2. C(s) C(g) H2 = Hf (C,g)
3. 4H(g) + C(g) CH4(g) H3 = Hatom
2H2(g) + C(s) CH4(g) H = Hf(CH4,g)

Calculating Hatom and Bond Energy
Hf(CH4,g) = 4Hf(H,g) + Hf(C,g) Hatom
Rearranging gives
Hatom= 4Hf(H,g) + Hf(C,g) Hf(CH4,g)
Look these up in Table 18.3, 6.2 or appendix C
Hatom= 4(217.9kJ/mol) + 716.7kJ/mol
(74.8kJ/mol)
Hatom= 1663.1 kJ/mol of CH4
1663.1 kJ/mol
bond energy
4
= 415.8 kJ/mol of CH bonds
Table 19.4 Some Bond Energies

Using Bond Energies to Estimate Hf
Calculate Hf for CH3OH(g) (bottom reaction)
Use 4 step path
Step 1 break CC bonds
Step 2 break HH bonds
Step 3: break OO bond
Step 4: form 4 CH bonds

Using Bond Energies
Hf(CH3OH,g) = Hf(C,g) + 4Hf(H,g) + Hf(O,g)
Hatom (CH3OH,g)
Hf(C,g) + 4Hf(H,g) + Hf(O,g)
= {716.7 +(4*217.9) + 249.2}kJ = +1837.5 kJ
Hatom (CH3OH,g) = 3DCH + DCO + DOH
= (3*412) + 360 + 463 = 2059 kJ
Hf(CH3OH,g) = +1837.5 kJ 2059 kJ = 222 kJ
Experimentally find Hf(CH3OH,g) = 201 kJ/mol
So bond energies give estimate within 10% of actual

CH19 Thermodynamics

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Chapter 19: Thermodynamics

Chemistry: The Molecular Nature of

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

E system (KE )system (PE )system

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 3

q + Heat absorbed by system Esystem

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4

E system (KE )system (PE )system

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

Bigger than most, but still small

Note: Assumes that volumes of solids and liquids are

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13

Volumes assuming each coefficient equal

= 13,898.9 kJ 29.0 kJ = 13,927.9 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 17

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 19

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 21

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22

Kinetics tells us:

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 31

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 32

For gases, Entropy as Volume

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35

A. water vapor condensing to liquid

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37

Higher positional Lower positional

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 40

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41

H2O(g) H2O() negative

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 42

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43

A. Ag+(aq) + Cl-(aq) AgCl(s)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 44

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 45

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 46

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 48

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 49

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 51

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 52

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 55

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 56

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 57

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 58

S = 56.5 J/K + 566.1 J/K 51.00 J/K

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 62

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 63

H = 0.0 kJ 725.4 kJ 0.00 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 65

Step 2: Calculate S see Ex. 4